CN101517759B - Method for manufacturing group iii nitride compound semiconductor light-emitting device, group iii nitride compound semiconductor light-emitting device, and lamp - Google Patents

Abstract

The invention provides a method for manufacturing a group III nitride compound semiconductor light-emitting device having excellent emission characteristics with excellent productivity, and also provides a group III nitride compound semiconductor light-emitting device and a lamp. In the method for manufacturing a group III nitride compound semiconductor light-emitting device, an intermediate layer (12) composed of at least a group III nitride compound is arranged on a substrate (11), and then an n-type semiconductor layer (14) comprising a foundation layer (14a), a light-emitting layer (15) and a p-type semiconductor layer (16) are sequentially arranged on the intermediate layer (12). This method comprises a pretreatment step for plasma processing the substrate (11) and a sputtering step following the pretreatment step for forming the intermediate layer (12) on the substrate (11) by a sputtering method.

Description

The manufacturing approach of III group-III nitride compound semiconductor light-emitting device

Technical field

The present invention relates to be suitable for manufacturing approach and the III group-III nitride compound semiconductor light-emitting device and the lamp of the III group-III nitride compound semiconductor light-emitting device of light-emitting diode (LED), laser diode (LD), electronic device etc.

The application is based on and required priority at the patent application 2006-260878 of japanese publication with on July 30th, 2007 patent application 2007-197473 number of japanese publication on September 26th, 2006, here cites its content.

Background technology

III group-III nitride compound semiconductor light-emitting device has the band gap of the energy Direct Transfer type of the scope that is equivalent to from the visible light to the ultraviolet region, and luminous efficiency is excellent, therefore uses as light-emitting components such as LED and LD.

In addition, even be used for the occasion of electronic device, III group-III nitride compound semiconductor light-emitting device is compared with the situation of in the past use III-V family (the 3rd main group～the 5th main group) compound semiconductor, also can obtain having the electronic device of excellent specific property.

In the past, as the single-crystal wafer of III-V compound semiconductor, generally be to be employed in the crystallization (crystal of growing on the single-crystal wafer of material different; Crystal) method that obtains.Between such dissimilar substrate (substrate) and the crystallization of epitaxially grown in the above III group-III nitride semiconductor, there is bigger lattice mismatch (Lattice Mismatch).For example, make gallium nitride (GaN) at sapphire (Al ₂O ₃) occasion of growing on the substrate, there is 16% lattice mismatch between, the occasion that gallium nitride is grown on the SiC substrate, and there is 6% lattice mismatch between.

Usually, there is the occasion of the big lattice mismatch of above-mentioned that kind, is difficult to make crystallization directly epitaxial growth on substrate, and, even also there is the problem that can not get the good crystallization of crystallinity in the occasion of growth.

Therefore; Once having proposed employing metal organic chemical vapor deposition (MOCVD) method makes the crystallization of III group-III nitride semiconductor on sapphire single crystal substrate or SiC monocrystal substrate during epitaxial growth; The at first range upon range of layer that is known as low temperature buffer layer that is formed by aluminium nitride (AlN) or AlGaN at high temperature makes the epitaxially grown method of III group-III nitride semiconductor crystallization (for example patent documentation 1,2) again on this low temperature buffer layer on substrate.

Yet; In patent documentation 1 and 2 described methods; Therefore because lattice mismatch between the III group-III nitride semiconductor crystallization of substrate and growth above that basically, become in the inside of the crystallization of having grown and be surrounded by the state that is called as the dislocation that runs through dislocation to the surface extension.Therefore, crystallization produces distortion, if do not make structure suitable, just can not obtain sufficient luminous intensity, and, there is the problem of productivity ratio reduction etc.

In addition, also once proposed to adopt MOCVD method film forming in addition to form the technology of above-mentioned resilient coating.

For example, the method (for example patent documentation 3) that adopts MOCVD that the crystallization of same composition is grown had once been proposed on the resilient coating of the film forming through high-frequency sputtering.Yet, patent documentation 3 described methods, existence can not be in the problem of the stable and good crystallization of substrate laminated.

Therefore; In order to obtain stable and good crystallization; Once after having proposed to make buffer growth, the method for in the mist that comprises ammonia and hydrogen, annealing (for example patent documentation 4) and under the temperature more than 400 ℃, form the method (for example patent documentation 5) etc. of resilient coating through the DC spatter film forming.In addition; In patent documentation 4,5, put down in writing: as the material that is used for substrate; Can enumerate sapphire, silicon, carborundum, zinc oxide, gallium phosphide, GaAs, magnesia, manganese oxide, III group-III nitride based compound semiconductor monocrystalline etc., wherein, sapphire a face substrate is optimum.

On the other hand, when on semiconductor layer, forming electrode, have as using Ar gas to carry out the method (for example patent documentation 6) of reverse sputtering to the preliminary treatment of semiconductor layer.It is said according to patent documentation 6 described methods, implement reverse sputtering, can improve the contact characteristics between semiconductor layer and the electrode through surface to III group-III nitride compound semiconductor layer.

Yet,, because lattice mismatch between substrate and the semiconductor layer, can not on substrate, form and have good crystalline semiconductor layer even the problem of existence is the preliminary treatment that patent documentation 6 described methods is applied to substrate.

Patent documentation 1: No. 3026087 communique of Japan Patent

Patent documentation 2: japanese kokai publication hei 4-297023 communique

Patent documentation 3: the special fair 5-86646 communique of Japan

Patent documentation 4: No. 3440873 communique of Japan Patent

Patent documentation 5: No. 3700492 communique of Japan Patent

Patent documentation 6: japanese kokai publication hei 8-264478 communique

Summary of the invention

As stated; Above-mentioned any method all is behind former state laminated resilient coating on the substrate; Make the method for III group-III nitride compound semiconductor epitaxial growth, therefore have lattice mismatch between substrate and the crystallization of III group-III nitride semiconductor, can not obtain the problem of stable and good crystallization.

The present invention accomplishes in view of above-mentioned problem; Its objective is that employing can form resilient coating with the method that the short time forms the crystalline film of good uniformity on substrate; And the good III group-III nitride semiconductor of crystallinity is grown on this resilient coating; Provide productivity ratio excellent, and have manufacturing approach and the III group-III nitride compound semiconductor light-emitting device and the lamp of the III group-III nitride compound semiconductor light-emitting device of the excellent characteristics of luminescence.

The result that the present inventor studies with great concentration in order to address the above problem finds: before utilizing sputtering method formation resilient coating; Suitably carry out the preliminary treatment of substrate; Substrate surface is exposed so that and III group-III nitride compound between the lattice structure coupling of crystallization; The crystallization of III group-III nitride semiconductor is obtained as stable good crystallization, thereby accomplished the present invention.

That is, the present invention relates to following scheme.

A kind of manufacturing approach of III group-III nitride compound semiconductor light-emitting device; It is the range upon range of at least intermediate layer that forms by III group-III nitride compound on substrate; And on this intermediate layer, stack gradually the manufacturing approach of the III group-III nitride compound semiconductor light-emitting device of n type semiconductor layer, luminescent layer and p type semiconductor layer with basalis; It is characterized in that having: the pretreatment process that aforesaid substrate is carried out plasma treatment; With after this pretreatment process, adopt sputtering method on aforesaid substrate, to form the sputtering process in above-mentioned intermediate layer.

Manufacturing approach according to [1] described III group-III nitride compound semiconductor light-emitting device is characterized in that, above-mentioned pretreatment process makes the gas that contains nitrogen carry out in indoor circulation.

Manufacturing approach according to [2] described III group-III nitride compound semiconductor light-emitting device is characterized in that, in the above-mentioned pretreatment process, is 1 * 10 in the above-mentioned dividing potential drop that contains the gas of nitrogen of above-mentioned indoor circulation ^-2The scope of～10Pa.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[3] is characterized in that the scope that it is 0.1～5Pa that above-mentioned pretreatment process makes above-mentioned indoor pressure is carried out.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[4] is characterized in that, it is that 30 seconds～3600 seconds scope is carried out that above-mentioned pretreatment process makes the processing time.

Manufacturing approach according to [5] described III group-III nitride compound semiconductor light-emitting device is characterized in that, it is that 60 seconds～600 seconds scope is carried out that above-mentioned pretreatment process makes the processing time.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[6] is characterized in that, it is that 25 ℃～1000 ℃ scope is carried out that above-mentioned pretreatment process makes the temperature of aforesaid substrate.

Manufacturing approach according to [7] described III group-III nitride compound semiconductor light-emitting device is characterized in that, it is that 300～800 ℃ scope is carried out that above-mentioned pretreatment process makes the temperature of aforesaid substrate.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[8] is characterized in that, at same indoor above-mentioned pretreatment process and the above-mentioned sputtering process of carrying out.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[9] is characterized in that the plasma treatment in the above-mentioned pretreatment process is a reverse sputtering.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[10] is characterized in that, above-mentioned pretreatment process is to utilize to have adopted high-frequency power supply to produce plasma, thereby carries out reverse sputtering.

Manufacturing approach according to [11] described III group-III nitride compound semiconductor light-emitting device is characterized in that, above-mentioned pretreatment process comprises: utilize and adopted high-frequency power supply to produce nitrogen plasma, thereby carry out reverse sputtering.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[12] is characterized in that, forms above-mentioned intermediate layer with at least 90% the mode that covers the aforesaid substrate surface.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[13] is characterized in that, above-mentioned sputtering process uses the raw material that contains V group element.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[14]; It is characterized in that above-mentioned sputtering process adopts the reactive sputtering method that the raw material that contains V group element is circulated to form above-mentioned intermediate layer in reactor.

Manufacturing approach according to [14] or [15] described III group-III nitride compound semiconductor light-emitting device is characterized in that above-mentioned V group element is a nitrogen.

Manufacturing approach according to [14] or [15] described III group-III nitride compound semiconductor light-emitting device is characterized in that, uses ammonia as the above-mentioned raw material that contains V group element.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[17] is characterized in that, above-mentioned sputtering process is to adopt the RF sputtering method to form above-mentioned intermediate layer.

Manufacturing approach according to [18] described III group-III nitride compound semiconductor light-emitting device is characterized in that, above-mentioned sputtering process is to adopt the RF sputtering method, while the magnet of negative electrode is moved form above-mentioned intermediate layer.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[19] is characterized in that, above-mentioned sputtering process is that to make the temperature of aforesaid substrate be that 400～800 ℃ scope forms above-mentioned intermediate layer.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[20] is characterized in that, adopts mocvd method on above-mentioned intermediate layer, to form above-mentioned basalis.

According to [1]～20] the manufacturing approach of each described III group-III nitride compound semiconductor light-emitting device, it is characterized in that, adopt the reactive sputtering method on above-mentioned intermediate layer, to form above-mentioned basalis.

Manufacturing approach according to each described III group-III nitride compound semiconductor light-emitting device of [1]～[22] is characterized in that the temperature that makes aforesaid substrate is to form above-mentioned basalis more than 900 ℃.

A kind of III group-III nitride compound semiconductor light-emitting device; Be the intermediate layer that comprises III group-III nitride compound at least to be arranged in the substrate laminated; On this intermediate layer, stack gradually the III group-III nitride compound semiconductor light-emitting device of n type semiconductor layer, luminescent layer and p type semiconductor layer with basalis; It is characterized in that, aforesaid substrate be through plasma treatment preliminary treatment substrate, above-mentioned intermediate layer is the intermediate layer of adopting sputtering film-forming.

According to [24] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that above-mentioned intermediate layer forms as monocrystalline.

According to [24] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that above-mentioned intermediate layer forms as column crystallization.

According to [26] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that it is that the scope of 1～100nm forms that above-mentioned intermediate layer makes the mean value of width of each crystal grain of above-mentioned column crystallization.

According to [26] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that it is that the scope of 1～70nm forms that above-mentioned intermediate layer makes the mean value of width of each crystal grain of above-mentioned column crystallization.

Each described III group-III nitride compound semiconductor light-emitting device according to [24]～[28] is characterized in that, above-mentioned intermediate layer is to form with at least 90% the mode that covers the aforesaid substrate surface.

Each described III group-III nitride compound semiconductor light-emitting device according to [24]～[29] is characterized in that the thickness in above-mentioned intermediate layer is the scope of 10～500nm.

Each described III group-III nitride compound semiconductor light-emitting device according to [24]～[29] is characterized in that the thickness in above-mentioned intermediate layer is the scope of 20～100nm.

Each described III group-III nitride compound semiconductor light-emitting device according to [24]～[31] is characterized in that above-mentioned intermediate layer comprises the composition that contains Al.

According to [32] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that the intermediate layer, upper strata is formed by AlN.

Each described III group-III nitride compound semiconductor light-emitting device according to [24]～[33] is characterized in that above-mentioned basalis is formed by the GaN based compound semiconductor.

According to [34] described III group-III nitride compound semiconductor light-emitting device, it is characterized in that above-mentioned basalis is formed by AlGaN.

A kind of III group-III nitride compound semiconductor light-emitting device, it is to adopt each described manufacturing approach of above-mentioned [1]～[23] to obtain.

A kind of lamp, it has used each described III group-III nitride compound semiconductor light-emitting device of above-mentioned [24]～[36].

The invention effect

Manufacturing approach and III group-III nitride compound semiconductor light-emitting device according to III group-III nitride compound semiconductor light-emitting device of the present invention; Has the pretreatment process that substrate is carried out plasma treatment through becoming; And have after this pretreatment process, adopt sputtering method on aforesaid substrate, to form the above-mentioned formation of the sputtering process in intermediate layer; Can form intermediate layer at substrate surface, between substrate and the semiconductor layer that forms by III group-III nitride compound semiconductor, can not produce lattice mismatch with the high crystalline texture of uniformity.

Therefore, the good III group-III nitride semiconductor of crystallinity is grown on substrate, can access the productivity ratio excellence, and have the III group-III nitride compound semiconductor light-emitting device of the excellent characteristics of luminescence.

Description of drawings

Fig. 1 is the figure that an example of the III group-III nitride compound semiconductor light-emitting device that the present invention relates to is explained on pattern ground, is the skeleton diagram of the cross-section structure of expression laminated semiconductor.

Fig. 2 is the figure that an example of the III group-III nitride compound semiconductor light-emitting device that the present invention relates to is explained on pattern ground, is the skeleton diagram of expression planar structure.

Fig. 3 is the figure that an example of the III group-III nitride compound semiconductor light-emitting that the present invention relates to is explained on pattern ground, is the skeleton diagram of expression cross-section structure.

Fig. 4 is the skeleton diagram that the lamp of the III group-III nitride compound semiconductor light-emitting device formation that the present invention relates to is used in the explanation of pattern ground.

Fig. 5 is the figure that the embodiment of the III group-III nitride compound semiconductor light-emitting device that the present invention relates to is described, is the curve chart of the X ray half breadth data of expression GaN crystallization.

Fig. 6 is the figure that the embodiment of the III group-III nitride compound semiconductor light-emitting device that the present invention relates to is described, is the curve chart of the X ray half breadth data of expression GaN crystallization.

Fig. 7 is the figure that an example of the III group-III nitride compound semiconductor light-emitting device that the present invention relates to is explained on pattern ground, is the skeleton diagram that is illustrated in the structure in the intermediate layer of film forming on the substrate.

Fig. 8 is the figure of an example of the manufacturing approach of the III group-III nitride compound semiconductor light-emitting device that the present invention relates to of pattern ground explanation, is the skeleton diagram of the structure of expression sputter equipment.

The drawing reference numeral explanation

1-III group-III nitride compound semiconductor light-emitting device,

The 10-laminated semiconductor,

The 11-substrate,

The 11a-surface,

The 12-intermediate layer,

The 14-n type semiconductor layer,

The 14a-basalis,

The 15-luminescent layer,

The 16-p type semiconductor layer,

17-light transmission positive pole,

The 2-lamp.

Embodiment

Below, suitably with reference to Fig. 1～6 on one side the manufacturing approach of the III group-III nitride compound semiconductor light-emitting device that the present invention relates to and an execution mode of III group-III nitride compound semiconductor light-emitting device and lamp described on one side.

The manufacturing approach of the III group-III nitride compound semiconductor light-emitting device of this execution mode; Be in the range upon range of at least intermediate layer 12 that forms by III group-III nitride compound of substrate 11; And on this intermediate layer 12, stack gradually the method for n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16 with basalis 14a; Be to have substrate 11 is carried out the pretreatment process of plasma treatment, and have after this pretreatment process, adopt sputtering method on substrate 11, to form the method for the sputtering process in intermediate layer 12.

The manufacturing approach of this execution mode; Make the crystallization of III group-III nitride compound semiconductor on substrate 11 during epitaxial growth; In sputtering process; Have pretreatment process as the preceding operation that is used on substrate 11, forming the intermediate layer 12 that comprises III group-III nitride compound, in this pretreatment process, substrate 11 is carried out plasma treatment.Through substrate 11 is carried out plasma treatment, can make the good III group-III nitride semiconductor growth of crystallinity expeditiously.

In addition; The III group-III nitride compound semiconductor light-emitting device (the following light-emitting component that abbreviates as sometimes) that adopts the manufacturing approach of this execution mode to obtain has semiconductor laminated structure shown in Figure 1; This laminated semiconductor 10; Be range upon range of at least on substrate 11 intermediate layer 12 that is formed by III group-III nitride compound to be arranged, and on this intermediate layer 12, stack gradually n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16, and 12 laminated there is basalis 14a to form in the intermediate layer with basalis 14a; Substrate 11 be through plasma treatment preliminary treatment substrate, intermediate layer 12 is as the layer that adopts sputtering film-formings and summary constitutes.

In addition; The laminated semiconductor 10 of this execution mode; Example as shown in Figures 2 and 3 is such; Can constitute: have light transmission anodal 17 in p type semiconductor layer 16 laminated, on light transmission anodal 17, be formed with positive terminal pad 18, and on the n of n type semiconductor layer 14 type contact layer 14b, form expose the light-emitting component 1 that regional 14d laminated has negative pole 19.

Below, the pretreatment process and the sputtering process that have in the manufacturing approach to the III group-III nitride compound semiconductor light-emitting device of this execution mode detail.

[pretreatment process]

The plasma treatment of in the pretreatment process of this execution mode, carrying out is preferably carried out in the plasma of the gas of active plasma species such as the generation that contains nitrogen, oxygen etc.Wherein, special nitrogen.

In addition, the plasma treatment in the pretreatment process of this execution mode is preferably reverse sputtering.

In the pretreatment process of this execution mode,, act on to plasma particle efficient rate substrate 11 through between substrate 11 and chamber, applying voltage.

Be used for substrate 11 is carried out the unstrpped gas of plasma treatment, can constitute, the gas that also can use the gas that mixed several compositions to form by the gas that has only a kind of composition.Wherein, the dividing potential drop of the unstrpped gas of nitrogen etc. is preferably 1 * 10 ^-2The scope of～10Pa, the more preferably scope of 0.1～5Pa.When the dividing potential drop of unstrpped gas was too high, the energy that the plasma particle has reduced, and the pretreating effect of substrate 11 reduces.In addition, above-mentioned dividing potential drop is crossed when hanging down, and the energy that the plasma particle has is too high, sometimes substrate 11 is caused damage.

Carry out the pretreated time through plasma treatment, be preferably 30 seconds～3600 seconds scope of (1 hour).Processing time can not obtain the effect of plasma treatment than above-mentioned scope in short-term certainly, but when longer than above-mentioned scope, characteristic can not improve especially yet, instead operating efficiency is reduced.Carry out the scope of (1 minute)～600 seconds (10 minutes) that are more preferably 60 seconds of pretreated time through plasma treatment.

Temperature when carrying out plasma treatment, 25～1000 ℃ scope preferably, treatment temperature are crossed when low; Also bring into play effect deficiently even carried out plasma treatment, in addition, when treatment temperature is too high; Sometimes residual impairment on the substrate surface is more preferably 300 ℃～800 ℃ scope.

In the pretreatment process of this execution mode, the employed chamber of plasma treatment, can use with after the same chamber, chamber of using when forming the intermediate layer in the sputtering process stated, also can use other chamber.If make chamber of in pretreatment process, using and the chamber of in sputtering process, using is common formation; Then consider it is preferred from reducing manufacturing equipment cost aspect; In addition; Under the condition that is used for the intermediate layer film forming, carry out the occasion of reverse sputtering as plasma treatment, owing to can not change the needed time by the loss sputtering condition, so operating efficiency improves.

In the pretreatment process of this execution mode, preferably be used for the plasma of plasma treatment through the RF discharge generation, through by RF discharge generation plasma, also can implement preliminary treatment through plasma treatment for the substrate that forms by insulator.

Moreover, to the preliminary treatment that substrate 11 is implemented, also can adopt the method for wet type in the lump.For example, to the substrate of being processed by silicon, implement known in the past RCA washing methods etc., making substrate surface is that hydrogen is terminal, in the sputtering process of after in detail, stating thus, and the process stabilizing when on substrate, forming the intermediate layer.

In this execution mode; After in pretreatment process, substrate 11 being carried out plasma treatment; After the range upon range of intermediate layer 12 that forms by III group-III nitride compound in the sputtering process stated, on this intermediate layer 12, form and have the n type semiconductor layer 14 of basalis 14a, thus as after shown in the embodiment that states; The crystallinity of III group-III nitride semiconductor improves extraordinarily, and the characteristics of luminescence of light-emitting component improves.

As through substrate 11 is carried out the mechanism that plasma treatment can obtain above-mentioned effect; Can enumerate: the dirt through utilizing reverse sputtering to remove to be attached to substrate 11 surfaces etc., the surface of substrate 11 expose make its with III group-III nitride compound between the lattice structure of crystallization mate.

In addition, the pretreatment process of this execution mode, for: through the plasma treatment of in the atmosphere that is mixed with ion component, uncharged free radical composition, carrying out, the method for coming the surface of treatment substrate 11.

At this, when removing dirt etc. from the surface of substrate, for example supply with under the situation of ion component etc. to substrate surface separately, exist energy strong excessively, can cause damage to substrate surface, the problem that the quality of the crystallization of growing on the substrate is reduced.

In the pretreatment process of this execution mode; As stated; Through implementing to be employed in the plasma treatment method of carrying out in the atmosphere that is mixed with ion component and free radical composition; Make reactive material act on substrate 11, can be not cause damage and carry out removing of dirt etc. substrate 11 surfaces with appropriate energy.As the mechanism that can obtain this effect, can think: through using the few plasma of ratio of ion component, the damage that substrate surface is caused is inhibited, and can remove dirt through making action of plasma effectively in substrate surface, or the like.

[sputtering process]

The sputtering process of this execution mode is to adopt sputtering method on substrate 11, to form the operation in intermediate layer 12, for example, through utilizing plasma will contain the gas activation of raw metal and V group element and making its reaction, just can form intermediate layer 12.

Sputtering method generally can use through plasma is closed in the technology that improves plasma density in the magnetic field, efficient is improved, and moves through the position that makes magnet, can realize the interior homogenizing of face of the target of institute's sputter.The movement technique of concrete magnet can suitably select according to sputter equipment, for example, magnet is shaken or rotatablely moves.

Shake or the method for rotation etc. makes the magnet of negative electrode move the RF sputtering method that carries out film forming while adopting in this wise, narrate in the back details, the film forming efficiency when forming intermediate layer 12 in substrate 11 sides is excellent, is preferred from this point consideration.

In the RF sputter equipment 40 of example shown in Figure 8, magnet 42 is configured in the below (below of Fig. 8) of metallic target 47, and this magnet 42 utilizes the illustrated drive unit of omission below metallic target 47, to shake.In chamber 41, supply with nitrogen and argon gas, on the substrate 11 that is installed on the heater 44, form the intermediate layer.At this moment, because magnet 42 shakes below metallic target 47 as above-mentioned, the plasma of therefore enclosing in the chamber 41 moves, and except the surperficial 11a of substrate 11, also can form the intermediate layer in zero deflection ground to side 11b.

In addition, adopt sputtering method to form the occasion in intermediate layer 12,, can enumerate pressure and nitrogen partial pressure in the stove as the important parameter beyond the temperature of substrate 11.

Pressure in the stove when adopting sputtering method to form intermediate layer 12 is preferably more than the 0.3Pa.Pressure in this stove is during less than 0.3Pa, and the amount of nitrogen is few, might not become nitride and is attached on the substrate 11 by the metal of sputter.Upper limit of pressure in this stove is not special to be limited, but need be suppressed at the pressure of the degree that can make the plasma generation.

In addition, at nitrogen (N ₂) add up to the ratio of the nitrogen in the flow to be preferably 20%～80% with Ar.The flow-rate ratio of nitrogen was less than 20% o'clock, and splash-proofing sputtering metal does not become nitride, might be attached on the substrate 11 with metallic state.The flow-rate ratio of nitrogen surpasses at 80% o'clock, and the amount of Ar tails off relatively, and sputtering rate reduces.At nitrogen (N ₂) nitrogen ratio in the flow that adds up to Ar is preferably 50%～80% scope especially.

Film forming speed when in addition, forming intermediate layer 12 is preferably the scope of second 0.01nm/ second～10nm/.Film forming speed is less than 0.01nm/ during second, and film can not become layer and grow into island, surface that might covered substrate 11, and film forming speed surpasses 10nm/ during second, and film does not become crystalline solid and becomes amorphous.

Moreover, when adopting sputtering method to form intermediate layer 12, preferably adopt the reactive sputtering method that V family raw material is circulated in reactor to carry out the method for film forming.

Usually, in sputtering method, the purity of target material is high more, the crystallinity of the film after the film forming etc. membranous good more.Adopt sputtering method to form the occasion in intermediate layer 12; Also can be used as the target material that becomes raw material and use III group-III nitride compound semiconductor; Utilize the plasma of the inert gas of Ar gas etc. to carry out sputter; But in the reactive sputtering method, be used for III family metal simple-substance of target material and composition thereof, comparing with III group-III nitride compound semiconductor can high-purityization.Therefore, in the reactive sputtering method, the crystallinity in the intermediate layer 12 of film forming is further improved.

The temperature of the substrate 11 when forming intermediate layer 12 is preferably 300～800 ℃ scope, more preferably 400～800 ℃ scope.The temperature of substrate 11 less than above-mentioned down in limited time, the intermediate layer can not covered substrate 11 whole, the possibility that exists substrate 11 surfaces to expose.The temperature of substrate 11 surpasses above-mentioned going up in limited time, and the migration of raw metal is too active, considers from the aspect as the function of resilient coating, might become inappropriate layer.

Adopting sputtering method with the raw metal plasmaization; When forming mixed crystal as the intermediate layer; The method that the existing metal that will become target is made as the mixture (can form alloy) of metal material in advance, the method that also can side by side carry out sputter for two targets preparing to form by material different.For example, under the situation of the film that forms definite composition, use the target of composite material, under the situation that forms several kinds of different films of composition, a plurality of targets are arranged at indoor getting final product.

As the nitrogen raw material that in this execution mode, uses, can have no and restrictedly use general known nitrogen compound, but ammonia, nitrogen (N ₂) because simple to operate, and can obtain more cheaply, be preferred therefore.

The decomposition efficiency of ammonia is good, can carry out film forming with the high speed of growth, but because reactive and toxicity height, therefore need remove the evil equipment and detector in addition, must make the material of the member that uses in the reaction unit be the high material of chemical stability.

In addition, using nitrogen (N ₂) as the occasion of raw material, as device can be easy to use device, but can not get high reaction speed.Yet, if for utilizing electric field, heat etc. that nitrogen is decomposed the method in the gatherer of back, can access than the low but film forming speed available degree on the commercial production of ammonia, if therefore consider with installation cost take into account nitrogen (N ₂) be most preferred nitrogenous source.

In addition, as stated, preferably the mode with the side of covered substrate 11 forms intermediate layer 12.And then, most preferably form intermediate layer 12 with the side of covered substrate 11 and the mode at the back side.Yet, adopt the occasion in film build method formation intermediate layer in the past, need be at most that the film forming about 6 times～8 times is handled, become long operation.As the film build method beyond this method, also can consider it to be arranged on indoor through not keeping substrate, the whole faces of substrate are carried out the method for film forming, but, worry that device becomes complicated in the occasion that need heat substrate.

Therefore, can consider aforesaid for example on one side through substrate being shaken or rotatablely move, Yi Bian and the method for carrying out film forming is changed with respect to the sputter direction of filmogen in the position that makes substrate.Through adopting such method, can carry out film forming in the surface and the side of substrate with operation once, then, and through being directed against the film formation process of substrate back, can be to add up to twice whole faces of operation covered substrate

In addition, also can adopt: the filmogen source constitutes for what taken place by large-area generation source, and moves through the occurrence positions that makes material, substrate is moved and on the whole faces of substrate, carries out the method for film forming.As such method, can enumerate: such as stated on one side through magnet being shaken or rotatablely moving, Yi Bian and make the position of the magnet of negative electrode in target, move the RF sputtering method that carries out film forming.In addition, adopt such RF sputtering method to carry out the occasion of film forming, also can adopt the method that substrate-side and cathode side are moved.In addition, if through will as the cathode arrangement in the generation source of material near substrate, not being that the plasma that takes place is supplied with to substrate with pencil, but the formation for supplying with the mode that substrate is encased, then substrate surface and side can the while film forming.

Moreover; As the method that produces plasma; Except applying under the specific vacuum degree the sputtering method that high voltage discharges as this execution mode, the laser that shines high-energy-density in addition produces the PLD method of plasma, produces quite a few kinds of methods such as PED method of plasma through irradiating electron beam, but wherein; Because sputtering method is the easiest and be suitable for production in enormous quantities, therefore can be described as preferable methods.Moreover in the occasion of using the DC sputter, existing causes target surface charging, the unsettled possibility of film forming speed, and therefore pulsed D C sputtering method or aforesaid RF sputtering method are adopted in expectation.

In the sputtering process of this execution mode; In pretreatment process, implemented on the substrate of reverse sputtering; Adopt sputtering method to form the intermediate layer, therefore between substrate and the crystallization of III group-III nitride semiconductor, do not produce lattice mismatch, can access the stable and good intermediate layer of crystallinity.

Below employing is had a light-emitting component 1 that the manufacturing approach of III group-III nitride compound semiconductor light-emitting device of this execution mode of aforesaid pretreatment process and sputtering process obtains formation detail.

[substrate]

In this execution mode; As the substrate 11 of epitaxial growth III group-III nitride compound semiconductor crystallization from the teeth outwards; Not special the qualification; Can select various materials to use, for example can enumerate sapphire, SiC, silicon, zinc oxide, magnesia, manganese oxide, zirconia, manganese oxide zinc-iron, oxidation magnalium, zirconium boride, gallium oxide, indium oxide, lithia gallium, lithia aluminium, neodymia gallium, lanthana strontium aluminium tantalum, strontium oxide strontia titanium, titanium oxide, hafnium, tungsten, molybdenum etc.Preferred especially sapphire.

Moreover; Do not form the intermediate layer not using ammonia; And the basalis of stating after method that adopt to use ammonia forms, and, use among the aforesaid substrate material, known through at high temperature contacting the occasion of the oxide substrate that causes chemical modification or metal substrate etc. with ammonia; The intermediate layer of this execution mode plays a role as coating, and is therefore more effective aspect the chemical modification that prevents substrate.

[intermediate layer]

The laminated semiconductor 10 of this execution mode adopts sputtering method to be formed with the intermediate layer 12 of the monocrystalline that is formed by III group-III nitride compound on substrate 11.Sputtering method is adopted in intermediate layer 12, for example through raw metal and the gas that contains V group element by plasma-activated, react and film forming.

Intermediate layer 12 needs more than at least 60% of surperficial 11a of covered substrates 11, preferably covers more than 80%, considers from the function aspects as basic 11 coating, preferably forms with the mode that covers more than 90%.In addition, most preferably intermediate layer 12 forms with the mode that the surperficial 11a with substrate 11 upward covers very close to each otherly.

When thereby intermediate layer 12 did not have the surface of covered substrate 11 substrates 11 to expose, film forming with directly the lattice constant of the basalis 14a of film forming on substrate 11 can be different, did not therefore become uniform crystallization in the basalis 14a on the intermediate layer 12, produces hillock or pit.

Moreover; In above-mentioned sputtering process; When on substrate 11, forming the intermediate layer, the intermediate layer 12a of example that can be shown in Fig. 7 (a) is such, forms with the mode of the surperficial 11a of a covered substrate 11; But intermediate layer 12b that also can be shown in Fig. 7 (b) is such, forms with the surperficial 11a of covered substrate 11 and the mode of side 11b.In addition, from considering as the function aspects of coating, that kind of the intermediate layer 12c as Fig. 7 (c) shown in most preferably, the surperficial 11a of covered substrate 11, side 11b and back side 11c and form.

As stated; When adopting mocvd method; Sometimes unstrpped gas is around to the side or the back side of substrate; Arbitrary layer the occasion of each layer that is made up of the crystallization of III group-III nitride compound semiconductor of therefore after adopting mocvd method to form, stating, for fear of the reaction of unstrpped gas and substrate, preferably the intermediate layer 12c shown in Fig. 7 (c) constitutes the intermediate layer so that also can the protective substrate side or the back side suchly.

The crystallization that forms the III group-III nitride compound in such intermediate layer has the crystalline texture of hexagonal crystal system, can form single crystal film through the control membrance casting condition.In addition, the crystallization of III group-III nitride compound through controlling above-mentioned membrance casting condition, also can form by being the column crystallization that basic texture constitutes with hexagon prism.Moreover so-called column crystallization in this explanation is meant forming crystal boundary with adjacent intergranule and separating, and itself is the crystallization of column as vertical sectional shape.

Preferably mono-crystalline structures is considered from the buffering function aspects in intermediate layer 12.As stated, the crystallization of III group-III nitride compound has the crystallization of hexagonal crystal system, and forming with hexagon prism is basic tissue.The crystallization of III group-III nitride compound through the condition of control film forming etc., can be formed in the crystallization that direction is also grown in the face.On substrate 11, form the occasion in the intermediate layer 12 with such mono-crystalline structures, the pooling feature in intermediate layer 12 acts on effectively, and therefore the III nitride semiconductor layer of film forming becomes and has good orientation and crystalline crystalline film above that.

In addition; Form the occasion in intermediate layer at the polycrystalline that constitutes as aggregate by column crystallization; Consider that from function aspects the mean value of the width of each crystal grain of above-mentioned column crystallization is preferably the scope of 1～100nm, more preferably the scope of 1～70nm as resilient coating.As the aggregate of column crystallization and form the occasion in intermediate layer; For the crystallinity of the crystallizing layer that makes above that the III group-III nitride compound semiconductor that forms good; Suitably the width of each crystallization crystal grain of control column crystallization is preferably above-mentioned scope particularly.The width of such crystallization crystal grain can easily be measured through cross section tem observation etc.

In addition, in the occasion that forms the intermediate layer as polycrystalline, the crystal grain of crystallization is preferably the shape of aforesaid roughly column, and gather and cambium layer in the intermediate layer preferably crystal grain of column.

At this, the width of the crystal grain of explaining among so-called the present invention is the occasion of the aggregate of columnar grain in the intermediate layer, is meant the distance at the interface and the interface of crystallization.On the other hand, in the occasion that crystal grain exists with island, the width of so-called crystal grain is meant the length of diameter of the maximum of the face that crystallization crystal grain contacts with real estate.

The thickness in intermediate layer 12 is preferably the scope of 10～500nm, more preferably the scope of 20～100nm.

The thickness in intermediate layer 12 is during less than 10nm, becomes insufficient as the function of resilient coating.In addition, to form the occasion in intermediate layer above the thickness of 500nm, although do not change as the function of resilient coating, the film forming processing time is elongated, might the productivity ratio reduction.

Intermediate layer 12 is preferably the composition that contains Al, is preferably the formation that comprises AlN especially.

As the material that constitutes intermediate layer 12, so long as the III group-III nitride compound semiconductor of being represented by general formula AlGaInN, then any material all can use.And then, also can be for containing as the As of V family, the formation of P.

Making intermediate layer 12 is the occasion that contains the composition of Al, wherein, is preferably GaAlN, and this moment, the composition of Al was preferably more than 50%.

In addition, with the intermediate layer as the aggregate of column crystallization and the occasion that forms through becoming the composition that comprises AlN, can form the column crystallization aggregate expeditiously.

[laminated semiconductor]

As shown in Figure 1; The laminated semiconductor 10 of this execution mode, on substrate 11, being situated between has aforesaid intermediate layer 12 and range upon range of the light emitting semiconductor layer that comprises the n type semiconductor layer 14, luminescent layer 15 and the p type semiconductor layer 16 that are formed by nitride-based compound semiconductor is arranged.

In addition, n type semiconductor layer 14 has the basalis 14a that is formed by III group-III nitride compound semiconductor at least, and 12 laminated have basalis 14a in the intermediate layer.

On the basalis 14a that forms by III group-III nitride compound semiconductor, as stated, can form the range upon range of formation that laminated semiconductor as shown in Figure 1 10 that kind are arranged with functional crystallization laminated construction.For example, in the occasion of the semiconductor laminated structure that is formed for light-emitting component, can form range upon range ofly the n type alloy that is doped with Si, Ge, Sn etc. n type conductive layer, be doped with the p type conductive layer etc. of the p type alloy of magnesium etc.In addition, as material, luminescent layer etc. can use InGaN, and coating etc. can use AlGaN.Through on basalis 14a, further forming III group-III nitride compound semiconductor crystallizing layer in this wise, can make the wafer that is used to make Light-Emitting Diode, laser diode or electronic device etc. with semiconductor laminated structure with function.

Below laminated semiconductor 10 is detailed.

As nitride-based compound semiconductor, known a lot of by for example general formula Al _XGa _YIn _ZN _1-AM _A(0≤X≤1,0≤Y≤1,0≤Z≤1, and X+Y+Z=1.Symbol M is represented and the different V group element of nitrogen (N), 0≤A＜1) gallium nitride compound semiconductor of expression, also can have no in the present invention restrictedly use comprise gallium nitride compound semiconductor that these are known, by general formula Al _XGa _YIn _ZN _1-AM _A(0≤X≤1,0≤Y≤1,0≤Z≤1, and X+Y+Z=1.Symbol M is represented and the different V group element of nitrogen (N), 0≤A＜1) expression gallium nitride compound semiconductor.

Gallium nitride compound semiconductor except Al, Ga with the In, can also contain other III family element, also can contain elements such as Ge, Si, Mg, Ca, Zn, Be, P, As and B as required.In addition, be not limited to wittingly the element that adds, also contain sometimes and depend on membrance casting condition etc. and impurity that contains inevitably and the trace impurity that in raw material, reaction tube material, contains.

The growing method of these gallium nitride compound semiconductors is not special to be limited, and can use MOCVD (metal organic chemistry vapour phase deposition process), HVPE (hydride vapor growth method), the MBE known all methods that make nitride semiconductor growing such as (molecular beam epitaxies).As preferred growing method.Consider it is mocvd method from the viewpoint of film thickness monitoring property, the property produced in enormous quantities.In mocvd method, can use hydrogen (H as carrier gas ₂) or nitrogen (N ₂); Can use trimethyl gallium (TMG) or triethyl-gallium (TEG) as the Ga source of III family raw material; Can use trimethyl aluminium (TMA) or triethyl aluminum (TEA) as the Al source, can use trimethyl indium (TMI) or triethylindium (TEI), can use ammonia (NH as the N source of V family raw material as the In source ₃), hydrazine (N ₂H ₄) etc.In addition, as alloy, in the n type, can use monosilane (SiH as the Si raw material ₄) or disilane (Si ₂H ₆), can use germanium gas (GeH as the Ge raw material ₄), tetramethyl germanium ((CH ₃) ₄Ge), tetraethyl germanium (C ₂H ₅) ₄Ge) etc. organic germanium compounds.In the MBE method, the germanium of element state also can be used as the doped source utilization, in the p type, uses for example bis-cyclopentadienyl magnesium (Cp as the Mg raw material ₂Mg) or two ethyl cyclopentadienyl group magnesium (EtCp ₂Mg).

[n type semiconductor layer]

N type semiconductor layer 14 is layered on the above-mentioned intermediate layer 12 usually, is made up of basalis 14a, n type contact layer 14b and n type coating 14c.Moreover n type contact layer can double as be basalis and/or n type coating, but basalis can double as be n type contact layer and/or n type coating also.

[basalis]

Basalis 14a is formed by III group-III nitride compound semiconductor, and range upon range of ground film forming is on substrate 11.

As the material of basalis 14a, can use and intermediate layer 12 material different of film forming on substrate 11, but preferably by Al _xGa _1-xN layer (0≤x≤1 is preferably 0≤x≤0.5, more preferably 0≤x≤0.1) constitutes.

As the material that is used for basalis 14a, can use the III group-III nitride compound that contains Ga, promptly the GaN based compound semiconductor especially can preferably use AlGaN or GaN.

In addition; In the occasion that forms intermediate layer 12 as the aggregate of the column crystallization that forms by AlN; Need make the dislocation cyclisation inherit the crystallinity in intermediate layer 12 through migration to avoid basalis 14a former state ground; Can enumerate the GaN based compound semiconductor of the above-mentioned Ga of containing as such material, preferred especially AlGaN or GaN.

The thickness of basalis is preferably more than the 0.1 μ m, more preferably more than the 0.5 μ m, most preferably is more than the 1 μ m.When this thickness is above, obtain the good Al of crystallinity easily _XGa _1-XThe N layer.

In basalis 14a, can be as required, 1 * 10 ¹⁷～1 * 10 ¹⁹/ cm ³Scope in Doped n-type impurity, but also can undope (＜1 * 10 ¹⁷/ cm ³), consider preferably to undope from keeping good crystalline viewpoint.Do not limit as n type impurity is special, for example, can enumerate Si, Ge and Sn etc., preferably enumerate Si and Ge.

In the occasion of substrate 11 use conductive boards, 14a mixes to basalis, and electric current is longitudinally flowed in the layer structure of basalis 14a, can form the structure that electrode is set on the chip two sides of light-emitting component thus.

In addition; Use the occasion of insulating properties substrate at substrate 11; Be employed in the chip structure that is formed with electrode on the identical faces of chip of light-emitting component, therefore on substrate 11, be situated between intermediate layer 12 is arranged and range upon range of basalis 14a when being unadulterated crystallization crystallinity become good.

(film build method of basalis)

Below the film build method of the basalis of execution mode is described.

In this execution mode, can adopt above-mentioned method after forming intermediate layer 12 on the substrate 11, form the basalis 14a that constitutes by III group-III nitride compound semiconductor, but before forming this basalis 14a, need not carry out annealing in process especially.Yet; Usually carry out the occasion of the film forming of III group-III nitride compound semiconductor at the gas chemistry film build method that adopts MOCVD, MBE, VPE etc.; Via without the stabilization procedures of the temperature-rise period of film forming and temperature and handle; But, therefore as a result of produce the annealing effect sometimes owing in these processes, make the unstrpped gas of V family more in the situation of indoor circulation.

In addition, the carrier gas as this moment circulation can have no and restrictedly use general carrier gas, also can use widely used hydrogen, nitrogen in the gas chemistry film build method of MOCVD etc.Yet, in the occasion of using hydrogen as carrier gas, the intensification in more active hydrogen, possible chemical ground damages the flatness of crystallinity and crystal surface, the therefore preferred shortening processing time.

Do not limit as the method for range upon range of basalis 14a is special, as each above-mentioned method, use so long as the crystalline growth method that the cyclisation of dislocation is produced just can have no restrictedly.Especially mocvd method, MBE method, VPE method can produce aforesaid migration, therefore can form the good film of crystallinity, thereby preferred.Wherein, mocvd method can access the best film of crystallinity, puts and can more preferably use from this.

In addition, also can adopt sputtering method to form the basalis 14a that constitutes by III group-III nitride compound semiconductor.In the occasion that adopts sputtering method, compare with mocvd method, MBE method etc., can make device become simple formation.

When adopting sputtering method to form basalis 14a, be preferably and adopt the reactive sputtering method that V family raw material is circulated in reactor to carry out the method for film forming.

As stated, usually, in sputtering method, the purity of target material is high more, the crystallinity of the film after the film forming etc. membranous good more.Adopting sputtering method to form the occasion of basalis 14a; Use III group-III nitride compound semiconductor as the target material that becomes raw material; Utilize the plasma of the inert gas of Ar gas etc. to carry out sputter and also be fine, but in the reactive sputtering method, be used for III family metal simple-substance of target material and composition thereof; Compare with III group-III nitride compound semiconductor, can high-purityization.Therefore, when adopting the reactive sputtering method, the crystallinity of the basalis 14a of film forming is further improved.

The temperature of the substrate 11 when forming basalis 14a, that is, the growth temperature of basalis 14a is preferably more than 800 ℃, is more preferably the temperature more than 900 ℃, most preferably is the temperature more than 1000 ℃.This is because pass through to improve the temperature of the substrate 11 when forming basalis 14a, is easy to generate the migration of atom, carries out the cyclisation of dislocation easily.In addition, the temperature of the substrate 11 when forming basalis 14a need be the low temperature of temperature of decomposing than crystal, therefore is preferably less than 1200 ℃.If the temperature of the substrate 11 when forming basalis 14a just can obtain the good basalis 14a of crystallinity in the said temperature scope.

In addition, the pressure in the MOCVD reactors preferably is adjusted to 15～40kPa.

[n type contact layer]

As n type contact layer 14b, with basalis 14a likewise preferably by Al _xGa _1-xN layer (0≤x≤1 is preferably 0≤x≤0.5, further is preferably 0≤x≤0.1) constitutes.In addition, preferably be doped with n type impurity, when with 1 * 10 ¹⁷～1 * 10 ¹⁹/ cm ³, preferably with 1 * 10 ¹⁸～1 * 10 ¹⁹/ cm ³Concentration when containing n type impurity, can keep with the good Ohmic contact of negative pole, suppress be full of cracks and take place, keep good crystallinity, be preferred from these aspects.Do not limit as n type impurity is special, for example can enumerate Si, Ge and Sn etc., preferably Si and Ge.Growth temperature is identical with basalis.

Constitute the preferably same composition of gallium nitride compound semiconductor of basalis 14a and n type contact layer 14b, their thickness of total is set at 1～20 μ m, be preferably set to 2～15 μ m, further be preferably set to the scope of 3～12 μ m.When thickness is this scope, can keep semi-conductive crystallinity well.

Preferably n type contact layer 14b and after n type coating 14c is set between the luminescent layer 15 stated.Through n type coating 14c is set, can remedy the deterioration of the flatness that the surface of n type contact layer 14b produces.N type coating 14c can be formed by AlGaN, GaN, GaInN etc.In addition, also can become the heterojunction of these structures or repeatedly range upon range of superlattice structure.In the occasion that is GaInN, much less, preferably the band gap than the GaInN of luminescent layer 15 is big.

[n type coating]

The thickness of n type coating 14c is not special to be limited, and the scope of 5～500nm preferably is more preferably the scope of 5～100nm.

In addition, the n type concentration of dopant of n type coating 14c is preferably 1 * 10 ¹⁷～1 * 10 ²⁰/ cm ³Scope, be more preferably 1 * 10 ¹⁸～1 * 10 ¹⁹/ cm ³Scope.

When concentration of dopant is this scope, can keep good crystallinity and the operating voltage that reduces light-emitting component, be preferred from this aspect.

< p type semiconductor layer >

P type semiconductor layer 16 is made up of p type coating 16a and p type contact layer 16b usually.Yet p type contact layer also can doublely be done p type coating.

[p type coating]

As p type coating 16a, so long as the composition bigger than the band-gap energy of luminescent layer 15, and can charge carrier be enclosed the p type coating in the luminescent layer 15, just not special the qualification can preferably be enumerated Al _dGa _1-dN (0＜d≤0.4, preferred 0.1≤d≤0.3) layer.When p type coating 16a was formed by such AlGaN, the aspect was preferred from charge carrier inclosure luminescent layer 15.The thickness of p type coating 16a is not special to be limited, and preferably 1～400nm is more preferably 5～100nm.The p type concentration of dopant of p type coating 16a is preferably 1 * 10 ¹⁸～1 * 10 ²¹/ cm ³, be more preferably 1 * 10 ¹⁹～1 * 10 ²⁰/ cm ³When p type concentration of dopant is above-mentioned scope, does not make the crystallinity reduction and can obtain good p type crystallization.

[p type contact layer]

As p type contact layer 16b, be to comprise Al at least _eGa _1-eThe gallium nitride system compound semiconductor layer of N (0≤e＜0.5 is preferably 0≤e≤0.2, more preferably 0≤e≤0.1).When the Al component is above-mentioned scope, can keep good crystallinity and with the p Ohmic electrode (with reference to after the optically transparent electrode 17 stated) ohmic contact well, consider it is preferred from this aspect.

In addition, with 1 * 10 ¹⁸～1 * 10 ²¹/ cm ³When the concentration of scope contains p type alloy, can keep good Ohmic contact, prevent to chap, keep good crystallinity, consider it is preferred from these aspects, be more preferably 5 * 10 ¹⁹～5 * 10 ²⁰/ cm ³Scope.

Do not limit as p type impurity is special, for example preferably enumerate Mg.

The thickness of p type contact layer 16b is not special to be limited, and is preferably 10～500nm, more preferably 50～200nm.When thickness is this scope, more satisfactory aspect luminous power output.

< luminescent layer >

Luminescent layer 15 be on being laminated in n type semiconductor layer 14 in; The range upon range of above that layer that p type semiconductor layer 16 is arranged; As shown in Figure 1; Barrier layer 15a that is formed by gallium nitride compound semiconductor and the trap layer 15b that is formed by the gallium nitride compound semiconductor that contains indium are alternately range upon range of repeatedly, and, be disposed at the sequential cascade of n type semiconductor layer 14 sides and p type semiconductor layer 16 sides and form by barrier layer 15a.

In addition, in the example that Fig. 1 representes, luminescent layer 15 is following formation: the trap layer 15b of 6 layers barrier layer 15a and 5 layers is alternately range upon range of repeatedly, and barrier layer 15a is configured to the superiors and the orlop of luminescent layer 15, between each barrier layer 15a, disposes trap layer 15b.

As barrier layer 15a, for example, can preferably use band-gap energy than the big Al of trap layer 15b that forms by the gallium nitride compound semiconductor that contains indium _cGa _1-cThe gallium nitride compound semiconductor of N (0≤c＜0.3) etc.

In addition, in trap layer 15b,, can use for example Ga as the gallium nitride compound semiconductor that contains indium _1-sIn _sThe indium gallium nitride of N (0＜s＜0.4) etc.

[light transmission is anodal]

Light transmission anodal 17 is electrodes of the light transmission of formation on the p type semiconductor layer 16 of the laminated semiconductor of as above-mentioned, making 10.

Do not limit as the material of light transmission anodal 17 is special, the customary way that can be employed in this known is provided with ITO (In ₂O ₃-SnO ₂), AZO (ZnO-A1 ₂O ₃), IZO (In ₂O ₃-ZnO), GZO (ZnO-Ga ₂O ₃) material that waits.In addition, about its structure, also can have no restrictedly to use to comprise that the light transmission of any structure of known structure was anodal in the past.

Light transmission positive pole 17 can form with the mode with the roughly whole covering on the p type semiconductor layer 16 of doped with Mg, also can separate the gap and form with trellis or tree shape.After forming light transmission anodal 17, implement sometimes with alloying, the transparent thermal annealing that turns to purpose, but also can not implement.

[positive terminal pad and negative pole]

Positive terminal pad 18 is the electrodes that are formed on the above-mentioned light transmission anodal 17.

Material as positive terminal pad 18 uses the various structures of Au, Al, Ni and Cu etc. well-known, can have no the positive terminal pad of restrictedly using these well-known materials, structure.

The thickness of positive terminal pad 18 is preferably in the scope of 100～1000nm.In addition, on the characteristic of pad, when thickness was big, zygosity was high, so the thickness of positive terminal pad 18 is more preferably more than the 300nm.And then, consider from the viewpoint of manufacturing cost, be preferably below the 500nm.

Negative pole 19, with the semiconductor layer that on substrate 11, stacks gradually n type semiconductor layer 14, luminescent layer 15 and p type semiconductor layer 16 in, mode that the n type contact layer 14b of n type semiconductor layer 14 contacts forms.

For this reason, when forming negative terminal pad 17, remove the part of luminescent layer 15, p type semiconductor layer 16 and n type semiconductor layer 14 and form the regional 14d that exposes of n type contact layer 14b, on this zone, form negative pole 19.

As the material of negative pole 19, the negative pole of various The Nomenclature Composition and Structure of Complexes is well-known, can have no restrictedly to use these well-known negative poles, and the customary way that can be employed in this known is provided with.

As described above; Manufacturing approach according to the III group-III nitride compound semiconductor light-emitting device of this execution mode; Through for having a pretreatment process that substrate 11 is carried out plasma treatment; And have after this pretreatment process, adopt sputtering method on substrate 11, to form the formation of the sputtering process in intermediate layer 12; Can form intermediate layers 12 on substrate 11 surface, between substrate 11 and the semiconductor layer that forms by the III group-III nitride semiconductor, can not produce lattice mismatch with the high crystalline texture of uniformity.Therefore, can make the growth expeditiously on substrate 11 of the good III group-III nitride semiconductor of crystallinity, the III group-III nitride compound semiconductor light-emitting device 1 that can access the productivity ratio excellence and have the excellent characteristics of luminescence.

As stated; As the mechanism that can obtain above-mentioned effect through substrate 11 is implemented reverse sputtering; Can enumerate: the dirt etc. that is attached to substrate 11 surface is exposed in the plasma gas; Be removed through chemical reaction, the lattice structure coupling that makes crystallization between itself and the III group-III nitride compound is exposed on the surface of substrate 11 thus.

Manufacturing approach according to this execution mode; Through above-mentioned effect; Different with the method for for example using Ar gas to impact to remove the dirt on the substrate that is called as bombardment etc. through physical property, can not cause damage to substrate, can make substrate is that the surface of good state is implemented preliminary treatment.

Moreover; The formation of substrate of explaining in this execution mode and intermediate layer and basalis; Be not limited to III group-III nitride compound semiconductor light-emitting device; When for example using the close material of lattice constant to carry out film forming etc., at high temperature unstrpped gas and the substrate occasion that might react can have no restrictedly and use.

[lamp]

Can adopt the known means of those skilled in the art to constitute lamp through with III group-III nitride compound semiconductor light-emitting device that the present invention relates to as described above and fluorophor combination.Made up the technology that changes illuminant colour with regard to known through light-emitting component and fluorophor in the past, and can have no and restrictedly adopt such technology.

For example, through suitable selected fluorophor, can access than long luminous of light-emitting component wavelength, in addition, the emission wavelength through making light-emitting component itself and by the wavelength mixing of fluorophor conversion can be processed the alight that is white in color.

In addition, as lamp, can be used for any purposes of lateral emitting (side view) type of general purpose bullet cut, portable backlight purposes, positive luminous (top view) type that display uses etc.

For example; Example as shown in Figure 4 is such; To be assembled into the occasion of bullet cut with the III group-III nitride compound semiconductor light-emitting device 1 of an electrode type, one (Fig. 4 middle frame 21) in light-emitting component 1 and 2 frameworks is bonding, in addition; Adopt metal wire 24 that the negative pole (with reference to the symbol of representing among Fig. 3 19) of light-emitting component 1 is engaged with framework 22, adopt metal wire 23 that the positive terminal pad (with reference to the symbol of representing among Fig. 3 18) of light-emitting component 1 is engaged with framework 21.And,, can process the lamp 2 of the bullet cut of representing like Fig. 4 through the mold 25 that forms by transparent resin peripheral moulding with light-emitting component 1.

In addition, the III group-III nitride compound semiconductor light-emitting device that the present invention relates to except above-mentioned light-emitting component, can also be used for the photo-electric conversion element of laser diode, photo detector etc. or the electronic device of HBT, HEMT etc. etc.

Embodiment

Below illustrate in greater detail the manufacturing approach and the III group-III nitride compound semiconductor light-emitting device of III group-III nitride compound semiconductor light-emitting device of the present invention through embodiment, but the present invention has more than and is limited to these embodiment.

Embodiment 1

In this example; On the c of the substrate of processing by sapphire 11 face; The aggregate that employing RF sputtering method forms the column crystallization that is made up of AIN on this intermediate layer 12, adopts mocvd method as intermediate layer 12; The layer that formation is made up of the GaN based semiconductor of non-doping obtains the sample of embodiment 1 as basalis 14a.

At first, with only one side being carried out mirror ultrafinish to the substrate of being processed by sapphire 11 that can be used in epitaxially grown degree, do not carry out the preliminary treatment of wet type etc. especially and import in the sputter.At this,, use the device that has the power supply of high frequency type and have position mobile mechanism in target that can make magnet as sputter equipment.

Then, in sputter equipment, substrate is heated to 750 ℃, only import nitrogen with the flow of 30sccm after, indoor pressure is remained on 0.08Pa, substrate 11 sides are applied the high frequency bias of 50W, make substrate 11 be exposed to (reverse sputtering) in the nitrogen plasma.The temperature of the substrate 11 of this moment is 500 ℃, and the processing time is 200 seconds.

Then, the temperature with substrate 11 remains on 500 ℃, importing argon gas and nitrogen in sputter equipment.Then; Metal A l target side is applied the high frequency bias of 2000W; Pressure in the stove is remained on 0.5Pa; Under the condition that Ar gas is circulated with 5sccm with 15sccm circulation, nitrogen (ratio of the nitrogen in gas is overall is 75%), on the substrate of processing by sapphire 11, form the intermediate layer 12 of the column crystallization that constitutes by AlN.The speed of growth of this moment is 0.12nm/ second.

Moreover, the magnet in the target, whenever all shaking when the reverse sputtering of substrate 11 and during film forming.

Then, the film forming speed according to measuring in advance carries out the processing of stipulated time, behind the AlN film (intermediate layer 12) of formation 50nm, stops plasma work, and the temperature of substrate 11 is reduced.

Then, from sputter equipment, take out the substrate 11 that is formed with intermediate layer 12, import in the MOCVD stove.Then, adopt mocvd method to make the sample that film forming has GaN layer (III group-III nitride semiconductor) by following step.

At first, substrate 11 is imported in the reacting furnace, in the spherical case of crossing through nitrogen replacement, substrate placed on the microscope carrier (suscepter) of the carbon system that heats usefulness in 11 years.Then, nitrogen is circulated in stove after, utilize heater to make the temperature of substrate 11 be warmed up to 1150 ℃.Affirmation substrate 11 is opened the valve of ammonia pipe arrangement behind 1150 ℃ temperature stabilization, begin the ammonia that in stove, circulates.Then, in stove, supply with the hydrogen contain the TMGa steam, in film forming on the intermediate layer on the substrate 11 12, the processing that the GaN based semiconductor that constitutes basalis 14a is adhered to.The amount of ammonia is regulated and is made that the V/III ratio is 6000.Carry out after the growth of about 1 hour above-mentioned GaN based semiconductor, switch the valve of the pipe arrangement of TMGa, stop the supply of raw material in reacting furnace, growth is stopped.Then, make the growth ending of GaN based semiconductor after, stop energising to heater, with the greenhouse cooling of substrate 11 to room temperature.

Through above operation; Make the intermediate layer 12 that on the substrate of processing by sapphire 11, forms the column crystallization that constitutes by AlN, on this intermediate layer 12, formed the sample of the embodiment 1 of the basalis 14a that form by the GaN based semiconductor non-doping, 2 μ m thickness.The substrate that takes out is water white mirror-like.

Then, (パ Na リ テ イ カ Le corporate system, model: X ' part) measures the X ray swing curve (XRC) of the GaN layer of the non-doping that is obtained by said method to use four crystallization X ray determinators.

This is measured and uses the Beta-ray X ray of Cu the source to take place as light source, is carrying out as (0002) face of the plane of symmetry with on as (10-10) face of asymmetric.Usually, in the occasion of III group-III nitride compound semiconductor, the XRC spectral line half breadth of (0002) face becomes flatness (the mosaic property of crystallization; Mosaicity) index, (10-10) the XRC spectral line half breadth of face becomes dislocation density (spirality; Twist) index.The result of this mensuration adopts the GaN layer of the non-doping that manufacturing approach of the present invention obtains, and in the mensuration of (0002) face, demonstrating half breadth is 100 seconds, and in the mensuration of (10-10) face, demonstrating half breadth is 320 seconds.

In addition; Make the membrance casting condition of intermediate layer 12, basalis 14a and above-mentioned same, make the data of X ray half breadth of the GaN crystallization of the occasion that substrate temperature among the membrance casting condition in intermediate layer 12, in the pretreatment process and processing time change be shown in Fig. 5 and Fig. 6.

Embodiment 2

In this example; Through with the same condition of embodiment 1 under in the GaN crystallization (basalis 14a) of non-doping of 6 μ m of film forming; Formation is the n type contact layer 14b of alloy with Ge; And then range upon range of each semiconductor layer, finally made the epitaxial wafer with epitaxial layer structure (laminated semiconductor 10) that III group-III nitride compound semiconductor light-emitting device as shown in Figure 1 is used.

This epitaxial wafer has following structure: have on the substrate of being processed by sapphire 11 of c face; Adopt with after embodiment 1 identical growing method formation has the intermediate layer 12 that is formed by AlN of columnar crystal structure, the basalis 14a that forms from the sequentially range upon range of GaN that 6 μ m are arranged of substrate 11 sides, have 1 * 10 by non-doping ¹⁹Cm ^-3The n type contact layer 14b that forms of the GaN of 2 μ m of electron concentration by doped with Ge, have 1 * 10 ¹⁸Cm ^-3Electron concentration 20nm by In _0.1Ga _0.9N type coating (n type coating 14c), luminescent layer (multi-quantum pit structure) 15, p type semiconductor layer 16; Said luminescent layer 15 is for to start from the GaN barrier layer laminated construction of GaN barrier layer finally, is that bed thickness is 6 layers the barrier layer 15a that is formed by GaN of 16nm and the In by non-doping that bed thickness is 3nm _0.2Ga _0.85 layers the trap layer 15b that N forms alternately cascades, said p type semiconductor layer 16 have 5nm by the Al that is doped with Mg _0.1Ga _0.9 P type coating 16a that N forms and the Al of thickness 200nm by doped with Mg _0.02Ga _0.98The p type contact layer 16b that N forms.

In the manufacturing of the wafer of epitaxial loayer with above-mentioned semiconductor light-emitting elements structure, on the substrate of processing by sapphire 11, form the operation in the intermediate layer 12 that forms by AlN with columnar crystal structure, adopt the step identical with embodiment 1.

Thereafter semiconductor laminated structure range upon range of also used identical MOCVD device, likewise carries out with the film forming of basalis 14a.

Through above step, made the epitaxial wafer that semiconductor light-emitting elements is used with epitaxial layer structure.At this, by the Al of doped with Mg _0.02Ga _0.98The p type contact layer 16b that N forms even be not used for the annealing in process with p type carrier activation, also shows p type characteristic.

Then; Using aforesaidly has the epitaxial wafer (with reference to the laminated semiconductor 10 of Fig. 1) of epitaxial layer structure in the substrate of being processed by sapphire 11 laminated, produces a kind of light-emitting diode (with reference to the light-emitting component 1 of Fig. 2 and Fig. 3) as semiconductor light-emitting elements.

At first, the wafer for making adopts known photoetching process at the Al by doped with Mg _0.02Ga _0.98On the surface of the p type contact layer 16b that N forms, form the light transmission anodal 17 that constitutes by ITO and on this light transmission positive pole, forms have from face side sequentially range upon range of the positive terminal pad 18 of titanium, aluminium, golden structure.In addition, the part of wafer is implemented dry ecthing, the regional 14d that exposes on the n type contact layer 14b is exposed.On this part, made and comprised Ni, Al, Ti, this negative pole of 4 layers 19 of Au.Through these operations, on wafer, made each electrode of the shape that has as shown in Figures 2 and 3.

To as above-mentioned, on p type semiconductor layer and n type semiconductor layer, be formed with the wafer of electrode; The rear side of substrate 11 is carried out grinding and grinding forms specular; Cut into the square foursquare chip of 350 μ m; Each electrode is carried up put on lead frame, link to each other with lead frame, be made for semiconductor light-emitting elements with gold thread.The forward current that between the electrode of the positive terminal pad 18 of this semiconductor light-emitting elements (light-emitting diode) and negative pole 19, circulates, the forward voltage of result under electric current 20mA is 3.0V.In addition, observe luminance through the light transmission anodal 17 of p side, the luminous glistening light of waves of result is long to be 470nm, and luminous power output demonstrates 15mW.About light-emitting diode, do not obtain the characteristics of luminescence of such light-emitting diode by the roughly whole making of the wafer made from can having deviation.

The reverse sputtering condition in the pretreatment process and the mensuration result of X ray half breadth and luminous power output are shown in below table 1.

Comparative example 1

In this example; On the c of the substrate of processing by sapphire face; Do not carry out the pretreatment process of reverse sputtering and on substrate, form the intermediate layer that constitutes by AlN; On this intermediate layer, adopt mocvd method to form the basalis 14a that constitutes by GaN, in addition, likewise produce semiconductor light-emitting elements with embodiment 2.

The semiconductor light-emitting elements of comparative example 1, the forward voltage under electric current 20mA are 3.0V, and emission wavelength is 470nm, but luminous power output is 10mW, compare with the semiconductor light-emitting elements of embodiment 2, and luminous power output is relatively poor.

In addition; Measure to adopt the X ray swing curve (XRC) of the basalis 14a that is made up of GaN of the method growth of comparative example 1, the result is in the mensuration of (0002) face, and demonstrating half breadth is 300 seconds; In the mensuration of (10-10) face, demonstrating half breadth is 500 seconds, shows that crystallinity is poor.

Embodiment 3～7 and comparative example 2～3

In embodiment 3～7 and comparative example 2～3, the reverse sputtering in the pretreatment process is the condition shown in the below table 1, in addition, likewise produces semiconductor light-emitting elements with embodiment 2.

The reverse sputtering condition in the pretreatment process and the mensuration result of X ray half breadth and luminous power output are shown in below table 1.

Embodiment 8

In this example, before forming the intermediate layer on the substrate of processing by Si (111),, utilize the Ar plasma that substrate is implemented reverse sputtering,, use the RF sputter equipment of rotating cathode formula to form the single crystalline layer that constitutes by AlGaN as the intermediate layer as pretreatment process.At this, the substrate temperature during sputter is 500 ℃.

Then, on above-mentioned intermediate layer,, adopt mocvd method to form the layer that constitutes by the AlGaN that is doped with Si, on this basalis, form film again with the same light-emitting component semiconductor laminated structure of embodiment 2 as basalis.At this moment, the Al component in intermediate layer is 70%, and the Al component of basalis is 15%.

Then, after the employing mocvd method carries out the growth of semiconductor light-emitting elements laminated construction, from reaction unit, take out wafer, the surface of wafer is a minute surface as a result.

With the wafer of making in this wise and embodiment 2 likewise as light-emitting diode chip for backlight unit.In this example, with each electrode be arranged on semiconductor side and substrate-side about.

Then, the forward current that between each electrode, circulates, the forward voltage of result under electric current 20mA is 2.9V.In addition, through the anodal luminance of observing of the light transmission of p side, emission wavelength is 460nm as a result.Luminous power output demonstrates 10mW.About light-emitting diode, do not obtain the characteristic of such light-emitting diode by the roughly whole making of the wafer made from can having deviation.

Reverse sputtering condition in the pretreatment process is shown in below table 1 with the mensuration result.

Embodiment 9

In this example, before forming the intermediate layer on the substrate of processing by ZnO (0001),, utilize O as pretreatment process ₂The plasma of gas is implemented reverse sputtering, adopts the DC sputter equipment to form the intermediate layer that is formed by AlN of column crystallization.At this, the substrate temperature during sputter is 750 ℃.

Then, adopt mocvd method on above-mentioned intermediate layer, to form the basalis that constitutes by the AlGaN that is doped with Ge, on this basalis, form again and the film of the light-emitting component semiconductor laminated structure that embodiment 2 is same.

The Al component of the basalis of this moment is 10%.In addition, in this example, the trial-production emission wavelength is near the green LED the 525nm, has increased the flow of the In raw material of luminescent layer.

Then, after the employing mocvd method carries out the growth of semiconductor light-emitting elements laminated construction, from reaction unit, take out wafer, the surface of wafer is a minute surface as a result.

With the wafer of making like this and embodiment 2 likewise as light-emitting diode chip for backlight unit.In this example, with each electrode be arranged on semiconductor side and substrate-side about.

Then, the forward current that between each electrode, circulates, the forward voltage of result under electric current 20mA is 3.3V.In addition, through the anodal luminance of observing of the light transmission of p side, emission wavelength is 525nm as a result, presents green emitting.In addition, luminous power output demonstrates 10mW.About light-emitting diode, do not obtain the characteristic of such light-emitting diode by the roughly whole making of the wafer made from can having deviation.

The reverse sputtering condition of the pretreatment process in embodiment 2～9 and the comparative example 1～3 and the mensuration result of X ray half breadth and luminous power output are shown in below table 1.

Table 1

Shown in above-mentioned each result; The sample of III group-III nitride compound semiconductor light-emitting device of the present invention (embodiment 1～9); The half breadth of the X ray swing curve (XRC) of the basalis 14a that is formed by the GaN of non-doping is 50～200 seconds a scope; Be the light-emitting component of comparative example 1～3 of 300～1000 seconds scope than the half breadth of the X ray swing curve (XRC) of basalis, the crystallinity of the semiconductor layer that is formed by III group-III nitride compound is brought up to unexistent so far degree extraordinarily.Can know in addition, the light-emitting component of embodiment 2～7, luminous power output is the scope of 13～15mW, and the luminous power output of the light-emitting component of comparative example 1～3 is 3～10mW, than comparative example 1～3, improves significantly.

Clearly know thus, III group-III nitride compound semiconductor light-emitting device of the present invention, productivity ratio is excellent, and has the excellent characteristics of luminescence.

Utilize possibility on the industry

The present invention is applicable to manufacturing approach, III group-III nitride compound semiconductor light-emitting device and the lamp of employed III group-III nitride compound semiconductor element in light-emitting diode (LED), laser diode (LD), the electronic device etc.

Among the present invention the expression number range " more than " and " following " include given figure.

Claims (16)

1. the manufacturing approach of an III group-III nitride compound semiconductor light-emitting device; It is the range upon range of at least intermediate layer that forms by III group-III nitride compound on sapphire substrate; And on this intermediate layer, stack gradually the manufacturing approach of the III group-III nitride compound semiconductor light-emitting device of n type semiconductor layer, luminescent layer and p type semiconductor layer with basalis; It is characterized in that having: the temperature that makes said substrate be 300～800 ℃ scope, make the processing time be 30 seconds～3600 seconds scope, make the gas that contains nitrogen in indoor circulation, utilize the pretreatment process that has adopted high-frequency power supply to produce nitrogen plasma and said substrate carried out reverse sputtering; With after this pretreatment process, adopt sputtering method on said substrate, to form the sputtering process in said intermediate layer.

2. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, in the said pretreatment process, is 1 * 10 in the said dividing potential drop that contains the gas of nitrogen of said indoor circulation ^-2The scope of～10Pa.

3. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 and 2 is characterized in that, the scope that it is 0.1～5Pa that said pretreatment process makes said indoor pressure is carried out.

4. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, it is that 60 seconds～600 seconds scope is carried out that said pretreatment process makes the processing time.

5. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, at same indoor said pretreatment process and the said sputtering process of carrying out.

6. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, forms said intermediate layer with at least 90% the mode that covers said substrate surface.

7. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, said sputtering process uses the raw material that contains V group element.

8. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 7 is characterized in that, said sputtering process adopts the reactive sputtering method that the raw material that contains V group element is circulated in reactor to form said intermediate layer.

9. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 7 is characterized in that said V group element is a nitrogen.

10. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 7 is characterized in that, uses ammonia as the said raw material that contains V group element.

11. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, said sputtering process is to adopt the RF sputtering method to form said intermediate layer.

12. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 11 is characterized in that, said sputtering process is to adopt the RF sputtering method, while the magnet of negative electrode is moved form said intermediate layer.

13. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, said sputtering process is that to make the temperature of said substrate be that 400～800 ℃ scope forms said intermediate layer.

14. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, adopts mocvd method on said intermediate layer, to form said basalis.

15. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, adopts the reactive sputtering method on said intermediate layer, to form said basalis.

16. the manufacturing approach of III group-III nitride compound semiconductor light-emitting device according to claim 1 is characterized in that, the temperature that makes said substrate is to form said basalis more than 900 ℃.

Images